N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives, and herbicidal compositions

ABSTRACT

Disclosed herein are N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives of the formula (I): ##STR1## wherein R 1  is CF 3 , COOH or CCl═CClCOOH, R 2  is H, Cl, C 1  -C 3  alkyl or C 1  -C 4  alkoxycarbonyl; Z is CH or N; X 1  is C 1  -C 3  alkyl, C 1  -C 3  alkoxyl or Cl; and X 2  is C 1  -C 3  alkyl or C 1  -C 3  alkoxyl, a process for the preparation thereof, and herbicidal compositions containing the N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives as active ingredients.

This is a division of application Ser. No. 07/473,768, filed Feb. 2,1990, now U.S. Pat. No. 5,059,238.

BACKGROUND OF THE INVENTION

1) Field of the Invention

The present invention relates to N-substituted-3-(substitutedhydrazino)benzenesulfonamide derivatives, a preparation process thereof,and herbicidal compositions containing the derivatives as activeingredients.

2) Description of the Related Art

Numerous compounds have heretofore been proposed as herbicides. Forexample, U.S. Pat. No.4,632,695, U.S Pat. No.4,664,695 and JapanesePatent Application Laid-Open (KOKAI) No. 129276/1987 disclose a widevariety of compounds, including N-substituted-3-substitutedbenzenesulfonamide derivatives containing NHC(CH₃)=CHCOCH₃,NHC(CH₃)=CHCOOCH₃, NHCH₃, OCH₂ CF₃ or SCH₂ CF₃ on the 3-position and apyrimidine ring or a 1,3,5-triazine ring on the nitrogen atom.

There have conventionally been strong demands for herbicides capable ofexhibiting reliable herbicidal activity even at such low applicationdosages as bringing about the advantage of reducing the amount presentin the environment, herbicides capable of exhibiting selectivity betweencrops and weeds irrespective of variations in environmental conditions,herbicides free from crop injury to the second crop in double cropping,etc. The present invention has been completed with a view toward meetingsuch demands.

The present inventors have found that compounds still unreported to dateand having a substituted hydrazino group on the 3-position ofbenzenesulfonamide as to the inclusion of NHC(CH₃)═CHCOCH₃,NHC(CH₃)═CH--COOCH₃, NHCH₃, OCH₂ CF₃ or SCH₂ CF₃ on the 3-position ofbenzenesulfonamide in the compounds disclosed in EP-A-116518 andJapanese Patent Application Laid-Open (KOKAI) No. 129276/1987 haveexcellent herbicidal activity, leading to the completion of the presentinvention.

SUMMARY OF THE INVENTION

Therefore, an object of the invention is to provide novel compoundswhich show excellent herbicidal activity.

Another object of the invention is to provide a process for preparingnovel compounds which show excellent herbicidal activity.

A further object of the invention is to provide intermediates useful inthe preparation of novel compounds which show excellent herbicidalactivity.

A still further object of the invention is to provide novel herbicidalcompositions which show excellent herbicidal activity.

A still further object of the invention is to provide a method forcontrolling monocotyledonous or dicotyledonous weeds on an agriculturalor nonagricultural land.

In one aspect of the invention, there is thus provided anN-substituted-3-(substituted hydrazino)benzenesulfonamide derivative ofthe formula (I): ##STR2## wherein R¹ is CF₃, COOH or CCl═CClCOOH, R² isH, Cl, C₁ -C₃ alkyl or C₁ -C₄ alkoxycarbonyl; Z is CH or N; X¹ is C₁ -C₃alkyl, C₁ -C₃ alkoxyl or Cl; and X² is C₁ -C₃ alkyl or C₁ -C₃ alkoxyl.

In another aspect of the invention, there is also provided a process forthe preparation of the above-described N-substituted-3-(substitutedhydrazino)benzenesulfonamide derivative, which comprises reacting a3-(substituted hydrazino)benzenesulfonamide derivative of the formula(II): ##STR3## wherein R¹ and R² have the same meanings as definedabove, with a phenylcarbamate derivative of the following formula (III):##STR4## wherein Z, X¹ and X² have the same meanings as defined above.

In a further aspect of the invention, there is also provided a3-(substituted hydrazino)benzenesulfonamide derivative useful as anintermediate in the preparation of the aboveN-substituted-3-(substituted hydrazino)benzenesulfonamide, which isrepresented by the following formula (II): ##STR5## wherein R¹ and R²have the same meanings as defined above.

In a still further aspect of the invention, there is also provided a3-hydrazinobenzenesulfonamide derivative useful as an intermediate inthe preparation of the above 3-(substituted hydrazino)benzenesulfonamideof the formula (II), which is represented by the following formula (V'):##STR6## wherein R² ' is H, C₁ -C₃ alkyl or C₁ -C₄ alkoxycarbonyl.

In a still further aspect of the invention, there is also provided aherbicidal composition comprising as an active ingredient theN-substituted-3-(substituted hydrazino)benzenesulfonamide derivative ofthe formula (I).

In a still further aspect of the invention, there is also provided amethod for the control of monocotyledonous or dicotyledonous weeds on anagricultural or non-agricultural land, which comprises applying to theagricultural or non-agricultural land the N-substituted-3-(substitutedhydrazino)benzenesulfonamide derivative of the formula (I) or aherbicidal composition comprising said derivative.

The N-substituted-3-(substituted hydrazino)benzenesulfonamidederivatives of the present invention, which are represented by theformula (I), have not been disclosed in any publications known to theinventors of the present application, exhibit reliable herbicidalactivity at low application dosages and show selectivity between cropsand weeds. The herbicidal compositions of the invention, which containthe above derivatives as effective ingredients, are suitableparticularly for controlling before or after germination dicotyledonousand/or monocotyledonous weeds in important crops, for example, such aswheat, rice, corn, soybean, cotton, beet, potato, tomato or the like.They are also usable for the control of weeds not only on agriculturallands such as upland fields, paddy fields and orchards but also onnon-agricultural lands such as athletic fields and factory sites.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Specific examples of the N-substituted-3(substitutedhydrazino)benzenesulfonamide derivative represented by the formula (I)in the invention include those shown in Table 1.

                  TABLE 1                                                         ______________________________________                                         ##STR7##                                                                     Com-                                                                          pound                                                                         No.    R.sup.1      R.sup.2   X.sup.1                                                                             X.sup.2                                                                             Z                                   ______________________________________                                        I-1    CF.sub.3     H         OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-2    COOH         H         OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-3    CF.sub.3     Cl        OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-4    COOH         Cl        OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-5    CF.sub.3     CH.sub.3  OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-6    COOH         CH.sub.3  OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-7    CF.sub.3     COOCH.sub.3                                                                             OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-8    COOH         COOCH.sub.3                                                                             OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-9    CF.sub.3     COOC.sub.2 H.sub.5                                                                      OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-10   COOH         COOC.sub.2 H.sub.5                                                                      OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-11   CF.sub.3     COOCH.sub.3                                                                             Cl    OCH.sub.3                                                                           CH                                  I-12   COOH         COOCH.sub.3                                                                             Cl    OCH.sub.3                                                                           CH                                  I-13   CF.sub.3     COOCH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3                                                                            CH                                  I-14   COOH         COOCH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3                                                                            CH                                  I-15   CF.sub.3     COOCH.sub.3                                                                             OCH.sub.3                                                                           CH.sub.3                                                                            CH                                  I-16   CF.sub.3     COOCH.sub.3                                                                             OCH.sub.3                                                                           CH.sub.3                                                                            N                                   I-17   COOH         COOCH.sub.3                                                                             OCH.sub.3                                                                           CH.sub.3                                                                            N                                   I-18   CClCClCOOH   Cl        OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-19   CClCClCOOH   COOCH.sub.3                                                                             OCH.sub.3                                                                           OCH.sub.3                                                                           CH                                  I-20   CF.sub.3     COOCH.sub.3                                                                             OCH.sub.3                                                                           OCH.sub.3                                                                           N                                   ______________________________________                                    

The N-substituted-3-(substituted hydrazino)benzenesulfonamidederivatives represented by the formula (I) can each be synthesized byreacting a 3-(substituted hydrazino)benzenesulfonamide derivative of theformula (II) and a phenylcarbamate derivative of the following formula(III) in the presence of a base and in an organic solvent in accordancewith the following reaction formula: ##STR8## wherein R¹, R², Z, X¹ andX² have the same meanings as defined above.

In the above reaction, N,N-dimethylacetamide, N-methylpyrrolidone,acetonitrile or the like can be used as an organic solvent. On the otherhand, diazabicyclooctane, diazabicyclononene, diazabicycloundecene orthe like can be used as a base.

The reaction is conducted at a temperature in a range of from -20° C. to100° C., preferably from 0° C. to 50° C. for a reaction period in arange of from 0.5 hour to 24 hours.

After completion of the reaction, the reaction mixture is added to anaqueous solution of dilute hydrochloric acid and the precipitate thusformed is collected by filtration. The precipitate is dried in air andthen purified by a purification technique such as reprecipitation orcolumn chromatography or by a washing technique, whereby the intendedN-substituted-3-(substituted hydrazino)benzenesulfonamide derivativerepresented by the formula (I) can be obtained with high purity.

The 3-(substituted hydrazino)benzenesulfonamide derivative representedby the formula (II), which is a preparation intermediate and is employedas the starting material in the above reaction, can be synthesized inaccordance with the following reaction formula, using as a startingmaterial a 3-aminobenzenesulfonamide derivative represented by thefollowing formula (IV): ##STR9## wherein R¹ and R² have the samemeanings as defined above.

Synthesis of the compound represented by the formula (II) in accordancewith the above-described reaction can be practiced in the followingmanner. The 3-hydrazinobenzenesulfonamide derivative represented by theformula (V)--which has been obtained by diazotizing the amino group ofthe compound represented by the formula (IV) and reducing thethus-diazotized derivative--is stirred together withtrifluoroacetaldehyde ethylhemiacetal, glyoxylic acid monohydrate ormucochloric acid at 30-120° C., preferably 70°-90° C. for 0.5-8 hours inacetic acid or propionic acid or at room temperature for 5-7 hours in 6N sulfuric acid. After completion of the reaction, the reaction productis collected from the reaction mixture by filtration or the reactionmixture is evaporated to dryness under reduced pressure and ifnecessary, is purified by washing, whereby the compound represented bythe formula (II) can be obtained with good purity.

The compound represented by the formula (IV), which was used in theabove reaction formula, can be obtained from the correspondingnitrobenzene derivative, for example, by using the process described inBull. Chem. Soc. Jpn., 55, 3824 (1982); or from the corresponding3-nitroaniline derivatives, for example, by the process described inChem. Ber., 90841 (1957) or J. Macromol. Sci. Chem., 1969, 941, namely,by synthesizing 3-nitrobenzenesulfonamide derivatives and then reducingthe nitro groups with SnC1₂ in methanol or ethanol containing 35%hydrochloric acid.

Further, the compound represented by the formula (III) can-b.e obtainedfrom phenyl chloroformate and the corresponding2-amino-4,6-di-substituted pyrimidine (or 1,3,5-triazine), for example,by the process described in European Patent Specification No. 238,070.

Specific examples of the compound represented by the formulae (II) anduseful as the above preparation intermediate are summarized in Table 2.

In addition, specific examples of the compound represented by theformula (V) are shown in Table 3.

                  TABLE 2                                                         ______________________________________                                         ##STR10##                                                                    Compound                                                                      No.          R.sup.1       R.sup.2                                            ______________________________________                                        II-1         CF.sub.3      H                                                  II-2         COOH          H                                                  II-3         CF.sub.3      Cl                                                 II-4         COOH          Cl                                                 II-5         CF.sub.3      CH.sub.3                                           II-6         COOH          CH.sub.3                                           II-7         CF.sub.3      COOCH.sub.3                                        II-8         COOH          COOCH.sub.3                                        II-9         CF.sub.3      COOC.sub.2 H.sub.5                                  II-10       COOH          COOC.sub.2 H.sub.5                                  II-11       HOOCCClCCl    Cl                                                  II-12       HOOCCClCCl    COOCH.sub.3                                        ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                         ##STR11##                                                                    Compound                                                                      No.           R.sup.2                                                         ______________________________________                                        V-1           H                                                               V-2           Cl                                                              V-3           CH.sub.3                                                        V-4           COOCH.sub.3                                                     V-5           COOC.sub.2 H.sub.5                                              ______________________________________                                    

The N-substituted-3-(substituted hydrazino)benzenesulfonamidederivatives exhibit reliable herbicidal activity at low applicationdosages and show selectively between crops and weeds. The herbicidalcompositions of the invention, which contain the above compound's aseffective ingredients, are therefore suitable for controlling eitherbefore or after emergence monocotyledonous weeds and/or dicotyledonousweeds in important crops such as wheat, rice, corn, soybean, cotton,beet, potato and tomato.

Exemplary dicotyledonous weeds which can be controlled by the herbicidesof the invention include Amaranthus, Bidens, Stellaria, Solanum,Abutilon, Convolyulus, Matricaria, Balium, Lindernia, etc.

Illustrative monocotyledonous weeds include Echinochloa, Setaria,Digitaria, Avena, Cyperus, Alisma, Monochoria, etc.

The herbicidal compositions of the invention may take any preparationforms such as wettable powder, emulsion, powder, granule and the like.Known agronomically-acceptable vehicles (diluents) and aids can be used.

The applicable places of the herbicides according to the invention rangefrom agricultural lands such as upland fields, paddy fields and orchardto non-agricultural lands such as athletic fields and factory sites.

EXAMPLES

The present invention will hereinafter be described by the followingexamples.

SYNTHESIS EXAMPLE 1 Synthesis of methyl2-[(4,6-dimethoxyopyrimidin-2yl)aminocarbonvlaminosulfonyl[-4-[(2,2,2-trifluoroethylidene)hydrazino]benzoate(Compound No. I-7)

At room temperature, 166 mg (0.5 mmol) of methyl2-(aminosulfonyl)-4-[(2,2,2-trifluoroethlidene)hydrazino]benzoate and137.5 mg (0.5 mmol) of phenyl (4,6-dimethoxypyrimidin-2-yl)carbamatewere dissolved in 1.5 ml of N,Ndimethylacetamide. Then, 86.1 mg of1,8-diazabicyclo [5.4.0]undec-7-ene were added, followed by stirring for5 minutes. The resultant mixture was allowed to stand for 15 hours.Thereafter, 0.2 ml of 35% hydrochloric acid was added to 20 ml of icewater, followed by the addition of the reaction mixture in 0.2 mlportions under stirring. After the reaction mixture was stirred for 20minutes, the resulting precipitate was collected by filtration and driedin air. Using dichloromethane as an eluent, the crude product waspurified by chromatography on a column of silica gel ("WAKO GEL C-300",trade name; product of Wako Pure Chemical Industries, Ltd.). The titlecompound was obtained as a white solid. Yield: 162 mg (64%). Meltingpoint: 201°-202° C. Its physicochemical properties are shown in Table 4.

SYNTHESIS EXAMPLE 2

Synthesis of methyl2-[(4,6-dimethoxy-1,3,5-triazin2-yl)aminocarbonylaminosulfonyl]-4-(2,2,2-trifluoroethylidene)hydrazino]benzoate (Compound No. I-20)

At room temperature, 166 mg (0.5 mmol) of methyl2-(aminosulfonyl)-4-[(2,2,2-trifluoroethlidene)hydrazino]benzoate and138 mg (0.5 mmol) of phenyl (4,6-dimethoxy1,3,5-triazin-2-yl)carbamatewere dissolved in 1.5 ml of N,N-dimethylacetamide. Then, 86.1 mg of1,8-diazabicyclo[5.4.0]undec-7-ene were added, followed by stirring for5 minutes. The resultant mixture was allowed to stand for 6 hours.Thereafter, 0.2 ml of 35% hydrochloric acid was added to 30 ml of icewater, followed by the addition of the reaction mixture in 0.2 mlportions under stirring. After the reaction mixture was stirred for 20minutes, the resulting precipitate was collected by filtration and driedin air. Using as an eluent a 1:9 mixed solvent of methyl acetate andbenzene, the crude product was purified by chromatography on a column ofsilica gel ("WAKO GEL C300", trade name; product of Wako Pure ChemicalIndustries, Ltd.). The title compound was obtained as a white solid.Yield: 103 mg (41%). Melting point: 117°-119° C. (foamed). Itsphysicochemical properties are shown in Table 4.

The other N-substituted-3-(substituted hydrazino)benzenesulfonamidederivatives shown in Table 1 were also synthesized in a similar mannerto Synthesis Example 1. Namely, after obtaining crude products by asimilar procedure to Synthesis Example 1, they were separately purifiedby chromatography on a silica gel column or washing. Physicochemicalproperties of each of the N-substituted-3(substitutedhydrazino)benzenesulfonamide derivatives are shown in Table 4.Incidentally, in Table 4 and in Tables 5 and 6 which will be givensubsequently, the abbreviations in the columns for NMR data have thefollowing meanings:

δ: (ppm), s: singlet, d: doublet, t: triplet,

δ: quartet, m: multiplet, dd: double doublet, br: broad.

Further, with respect to the individual N-substituted-3-(substitutedhydrazino)benzenesulfonamide derivatives, the solvents employed uponpurification thereof and the yields attained were as follows:

Compounds purified by column chromatography:

    ______________________________________                                        Compound No.                                                                              Solvent employed Yield (%)                                        ______________________________________                                        I-1         CH.sub.2 Cl.sub.2                                                                              49                                               I-7         CH.sub.2 Cl.sub.2                                                                              64                                               I-9         CH.sub.2 Cl.sub.2                                                                              59                                               I-11        CH.sub.2 Cl.sub.2                                                                              64                                               I-13        Methyl acetate + benzene                                                                       67                                               I-14        Methyl acetate + benzene                                                                       55                                               I-15        Methyl acetate + benzene                                                                       24                                               I-20        Methyl acetate + benzene                                                                       41                                               ______________________________________                                    

Compounds purified by washing:

    ______________________________________                                        Compound No.                                                                              Solvent employed Yield (%)                                        ______________________________________                                        I-2         CH.sub.2 Cl.sub.2                                                                              68                                               I-3         petroleum ether  93                                               I-4         CH.sub.2 Cl.sub.2 + petroleum ether                                                            79                                               I-5         petroleum ether  81                                               I-6         petroleum ether  62                                               I-8         CH.sub.2 Cl.sub.2 + petroleum ether                                                            70                                               I-10        CH.sub.2 Cl.sub.2                                                                              50                                               I-12        CH.sub.2 Cl.sub.2 + hexane                                                                     80                                               I-14        CH.sub.2 Cl.sub.2 + hexane                                                                     70                                               I-17        CH.sub.2 Cl.sub.2 + petroleum ether                                                            57                                               I-18        CH.sub.2 Cl.sub.2                                                                              55                                               I-19        CH.sub.2 Cl.sub.2                                                                              30                                               ______________________________________                                    

                                      TABLE 4                                     __________________________________________________________________________                Melting                                                                       Point                                                             Com-        or De-                                                            pound                                                                             MS(m/e) composition                                                       No. (A)*)                                                                             (B)**)                                                                            Point (°C.)                                                                  IR(KBr, cm.sup.-1)                                                                     NMR(δ)                                       __________________________________________________________________________    I-1 293 155 132-135                                                                             3300-2700, 1710,                                                                       CDCl.sub.3                                                                        3.947(6H, s)5.783(1H, s)7.068(1H, q,                                          4.27Hz)7.443-7.738(5H, m)                                  De-   1610, 1570, 1490,                                                                          8.536(1H, s) 12.701(1H, s)                                 composition                                                                         1450, 1370, 1250,                                                             1160, 1120, 580                                             I-2 --  155 168-170                                                                             3350-2500, 1710,                                                                       d.sub.6 -                                                                         3.908(6H, s)5.990(1H, s)7.179(1H,                                             s)7.374(1H, dd, 6.71Hz, 1.83Hz)                            De-   1600, 1570, 1490,                                                                      DMSO                                                                              7.482-7.533(2H, m)7.707(1H, s)10.548(1H,                                      s)11.468(1H, s)                                            composition                                                                         1450, 1360, 1310,                                                                          12.594br(2H, s)                                                  1220, 1200, 1160,                                                             580                                                         I-3 327 155 204-206                                                                             3420-2800, 1710,                                                                       d.sub.6 -                                                                         3.898(6H, s)5.990(1H, s)7.29(1H, d,                                           7.3Hz)7.430(1H, q, 4.2Hz)                                        1600, 1570, 1490,                                                                      DMSO                                                                              7.59(1H, dd, 7.3Hz, 1.4Hz)7.797(1H, d,                                        1.4Hz)10.65br(1H, s)                                             1440, 1370, 1350,                                                                          11.525(1H, s)13.019(1H, s)                                       1280, 1250, 1220                                            I-4 --  155 146-147                                                                             3300-2600, 1700,                                                                       d.sub.6 -                                                                         3.915(6H, s)6.020(1H, s)7.196(1H,                                             s)7.372(1H, dd, 8.55Hz, 2.44Hz)                            De-   1610, 1570, 1490,                                                                      DMSO                                                                              7.580(1H, d, 8.55Hz)7.878(1H, d,                                              2.44Hz)10.665br(1H, s)                                     composition                                                                         1450, 1360, 1290,                                                                          11.559(1H, s)12.994br(1H, s)13.011br(1H,                                      s)                                                               1220, 1200, 1160,                                                             1030, 820, 630, 580                                         I-5 307 155 187-189                                                                             3300-2600, 3280,                                                                       CDCl.sub.3                                                                        2.585(3H, s)3.954(6H, s)5.805(1H,                                             s)6.980(1H, q, 4.3Hz)                                      De-   2930, 1710, 1600,                                                                          7.221(1H, d, 8.5Hz)7.306(1H, s)7.394(1H,                                      dd, 8.5Hz, 1.5Hz)                                          composition                                                                         1570, 1490, 1450,                                                                          7.719(1H, d, 1.5Hz)8.414(1H, s)12.735(1H,                                     s)                                                               1360, 1240, 1160,                                                             1120, 760, 700, 590                                         I-6 --  155 149-152                                                                             3250, 3150-2600,                                                                       d.sub.6 -                                                                         2.504(3H, s)3.911(6H, s)6.020(1H,                                             s)7.155(1H, s)7.289-7.370(2H, m)                           De-   1710, 1610, 1570,                                                                      DMSO                                                                              7.782(1H, s)10.587(1H, s)11.417(1H,                                           s)12.508br(1H, s)                                          composition                                                                         1490, 1450, 1370,                                                                          12.728br(1H, s)                                                  1360, 1220, 1190,                                                             1170, 590                                                   I-7 351 155 201-202                                                                             3400-2800, 3260,                                                                       d.sub.6 -                                                                         3.762(3H, s)3.947(6H, s)6.010(1H,                                             s)7.366(1H, d, 8Hz)                                              3100, 2950, 1720,                                                                      DMSO                                                                              7.494(1H, q, 4.9Hz)7.765(1H, d,                                               8Hz)7.855(1H, s)10.631(1H, s)                                    1600, 1580, 1490,                                                                          11.771(1H, s)12.579(1H, s)                                       1450, 1370, 1350,                                                             1300, 1270, 1240,                                                             1190, 1170, 1110,                                                             890, 820, 630, 580                                          I-8 --  155 148-149                                                                             3400-2700, 1710,                                                                       d.sub.6 -                                                                         3.795(3H, s)3.950(6H, s)6.010(1H,                                             s)7.257(1H, s)                                             De-   1600, 1570, 1440,                                                                      DMSO                                                                              7.440(1H, dd, 8.55Hz, 1.83Hz)7.777(1H, d,                                     8.55Hz)7.903(1H, d,                                        composition                                                                         1370, 1350, 1270,                                                                          1.83Hz)10.638(1H, s)11.783(1H,                                                s)12.574(1H, s)12.750br(1H, s)                                   1230, 1210, 1190,                                                             1160, 1110, 580                                             I-9 365 155 125-128                                                                             3320-2700, 3280,                                                                       CDCl.sub.3                                                                        1.347(3H, t, 7.33Hz)4.010(6H, s)4.296(2H,                                     q, 7.33Hz)5.790(1H, s)                                     De-   1710, 1590, 1570,                                                                          7.107(1H, q, 4.27Hz)7.457(1H, s)7.491(1H,                                     dd, 8.54Hz, 2.44Hz)                                        composition                                                                         1490, 1440, 1350,                                                                          7.780(1H, d, 8.54Hz)7.865(1H, d,                                              2.44Hz)9.024(1H, s)12.662(1H, s)                                 1290, 1260, 1230,                                                             1190, 1160, 1110,                                                             630, 580                                                    I-10                                                                              --  155 138-140                                                                             3300-2600, 1710,                                                                       d.sub.6 -                                                                         1.237(3H, t, 7.33Hz)3.945(6H, s)4.222(2H,                                     q, 7.33Hz)6.003(1H, s)                                     De-   1600, 1570, 1490,                                                                      DMSO                                                                              7.250(1H, s)7.431(1H, dd, 8.55Hz,                                             1.83Hz)7.770(1H, d, 8.55Hz)                                composition                                                                         1450, 1360, 1270,                                                                          7.900(1H, d, 1.83Hz)10.634(1H,                                                s)11.759(1H, s)12.555(1H, s)                                     1240, 1220, 1200,                                                                          12.750br(1H, s)                                                  1170, 580                                                   I-11                                                                              351 159 144-146                                                                             3340, 1740, 1610,                                                                      CDCl.sub.3                                                                        3.881(3H, s)4.147(3H, s)6.495(1H,                                             s)7.169(1H, q, 3.66Hz)                                     De-   1580, 1470, 1375,                                                                          7.528(1H, dd, 8.55Hz, 2.44Hz)7.805(1H, d,                                     8.55Hz)7.872(1H, d, 2.44Hz)                                composed                                                                            1310, 1290, 1190,                                                                          7.894(1H, s)8.966(1H, s)12.198(1H, s)                            1130, 590                                                   I-12                                                                              --  159 140-143                                                                             3400-2800, 1730,                                                                       d.sub.6 -                                                                         3.788(3H, s)4.045(3H, s)6.879(1H,                                             s)7.250(1H, s)                                             De-   1590, 1580, 1450,                                                                      DMSO                                                                              7.442(1H, dd, 8.55Hz, 2.44Hz)7.792(1H, d,                                     8.55Hz)7.897(1H, d, 2.44Hz)                                composed                                                                            1360, 1295, 1275,                                                                          10.902(1H, s)11.771(1H, s)11.951br(1H,                                        s)12.750br(1H, s)                                                1125, 590                                                   I-13                                                                              351 123 154-158                                                                             3300-2700, 1730,                                                                       CDCl.sub.3                                                                        2.514(6H, s)3.878(3H, s)6.759(1H,                                             s)7.190(1H, q, 3.06Hz)                                     De-   1720, 1620, 1480,                                                                          7.521(1H, dd, 8.54Hz, 2.44Hz)7.765(1H, d,                                     8.54Hz)                                                    composed                                                                            1470, 1450, 1360,                                                                          8.275(1H, s)9.269(1H, s)13.370(1H, s)                            1310, 1290, 1260,                                                             1130, 600                                                   I-14                                                                              --  123 145-150                                                                             3400-2600                                                                              d.sub.6 -                                                                         2.435(6H, s)3.757(3H, s)7.016(1H,                                             s)7.245(1H, s)                                             De-   1750br, 1635,                                                                          DMSO                                                                              7.430(1H, dd, 7.94Hz, 1.83Hz)7.764(1H, d,                                     7.94Hz)7.886(1H, d, 1.83Hz)                                composed                                                                            1590, 1490, 1480,                                                                          10.602(1H, s)11.761(1H, s)12.750br(1H,                                        s)13.304(1H, s)                                                  1460, 1370, 1300,                                                             1270, 1190, 1150,                                                             610                                                         I-15                                                                              351 139 152-154                                                                             3300-2800, 1750,                                                                       CDCl.sub.3                                                                        2.492(3H, s)3.866(3H, s)3.986(3H,                                             s)6.295(1H, s)7.158(1H, q,                                 De-   1620, 1590, 1470,                                                                          3.05Hz)7.509(1H, dd, 8.54Hz,                                                  2.44Hz)7.775(1H, d, 8.54Hz)7.792(1H, s)                    composed                                                                            1450, 1370, 1310,                                                                          7.884(1H, d, 2.44Hz)9.227(1H, s)13.275(1H,                                    s)                                                               1280, 1260, 1130,                                                             600                                                         I-16                                                                              351 140 101-105                                                                             3300-2800, 1730,                                                                       CDCl.sub.3                                                                        2.633(3H, s)3.898(3H, s)4.086(3H,                                             s)7.194(1H, q, 3.66Hz)7.526                                De-   1610, 1570, 1450,                                                                          (1H, dd, 8.55Hz, 2.44Hz)7.804(1H, d,                                          8.55Hz)7.842(1H, d, 2.44Hz)                                composed                                                                            1360, 1300, 1270,                                                                          8.235(1H, s)9.154(1H, s)12.615(1H, s)                            1240, 1170, 1110,                                                             820, 590                                                    I-17                                                                              --  140 144-146                                                                             3350-2700, 1760,                                                                       d.sub.6 -                                                                         2.500(3H, s)3.803(3H, s)3.996(3H,                                             s)7.250(1H, s)7.453                                        De-   1630, 1600, 1480,                                                                      DMSO                                                                              (1H, dd, 8.54Hz, 2.44Hz)7.799(1H, d,                                          8.54Hz)7.891(1H, d, 2.44Hz)                                composed                                                                            1390, 1310, 1280,                                                                          11.085(1H, s)11.776(1H, s)12.513(1H,                                          s)12.75(1H, s)                                                   1200, 1180, 1150,                                                             850, 620                                                    I-18                                                                              --  155 142-144                                                                             3300-2700, 1720,                                                                       d.sub.6 -                                                                         3.915(6H, s)6.025(1H, s)7.321(1H, dd,                                         8.54Hz, 2.44Hz)                                            De-   1600, 1580, 1540                                                                       DMSO                                                                              7.563(1H, d, 8.54Hz)7.831(1H, d,                                              2.44Hz)8.795(1H, s)10.697(1H, s)                           composed                                                                            1500, 1450, 1360,                                                                          11.666(1H, s)13.02br(1H, s)H of COOH was                                      not observed.                                                    1260, 1220, 1170,                                                             1020, 810, 760,                                                               690, 590                                                    I-19                                                                              --  155 148-149                                                                             3300-2800, 1730,                                                                       d.sub.6 -                                                                         3.752(3H, s)3.947(6H, s)6.012(1H,                                             s)7.370(1H, d, 8.55Hz)                                     De-   1610, 1580, 1450,                                                                      DMSO                                                                              7.764(1H, d, 8.55Hz)7.875(1H, s)8.830(1H,                                     s)10.634(1H, s)                                            composed                                                                            1380, 1290, 1270,                                                                          11.898(1H, s)12.577(1H, s)H of COOH was                                       not observed.                                                    1250, 1220, 1170,                                                             1110, 1020, 590                                             I-20                                                                              351 156 117-119                                                                             3300, 3200-2800,                                                                       CDCl.sub.3                                                                        3.898(3H, s)4.110(6H, s)7.167(1H, q,                                          3.66Hz)                                                    De-   1730, 1600, 1570,                                                                          7.527(1H, dd, 8.55Hz, 1.33Hz)7.799(1H, d,                                     8.55Hz)7.845(1H, d, 1.83Hz)                                composed                                                                            1500, 1460, 1380,                                                                          8.111(1H, s)8.959(1H, s)12.261(1H, s)                            1360, 1300, 1270,                                                             1245, 1170, 1120,                                                             815, 590                                                    __________________________________________________________________________     ##STR12##                                                                     ##STR13##                                                                

SYNTHESIS EXAMPLE 3

Synthesis of preparation intermediate, methyl2-(aminosulfonyl)-4-[(2,2,2-trifluoroethylidene)hydrazino1benzoate(Compound No. II-7)

(1) Synthesis of methyl 2-(aminosulfonyl)-4-hydrazinobenzoate (CompoundNo. V-4):

To a mixture of 6 ml of 35% hydrochloric acid and 6 ml of water, 3 g ofmethyl 4-amino-2-(aminosulfonyl)benzoate were added, followed bystirring at room temperature for 5 minutes. The reaction mixture wasthen cooled with ice water, followed by the addition of 3 ml of anaqueous solution of 0.95 g of sodium nitrite under stirring over 2minutes to conduct diazotization.

In 6.52 ml of 35% hydrochloric acid, 6.78 g of stannous chloride weredissolved. The resulting solution was cooled with ice water and stirred,followed by the addition of the diazotized compound prepared above.

After the resultant mixture was stirred for 20 minutes, it was left overfor 15 hours in a refrigerator. The reaction mixture was thentransferred into a 3-beaker, to which 38 g of sodium bicarbonate werethen added under stirring to adjust the pH to 6. The mixture thusprepared was then extracted twice with 300 ml of methyl acetate. Theextract was dried over sodium sulfate, and methyl acetate was distilledoff to obtain a pale yellow solid. Yield: 2.76 g (86%). Melting point:168°-170° C. Its physicochemical properties are shown in Table 6.

(2) Synthesis of methyl2-(aminosulfonyl)-4-(2,2,2trifluoroethylidene)hydrazino]benzoate(Compound No. II-7):

In 4 ml of acetic acid, 367.5 ml (1.5 mmol) of the compound synthesizedin the above procedure (1) (Compound No. V-4) and 0.21 ml oftrifluoroacetaldehyde ethylhemiacetal were dissolved, followed bystirring at 80° C. for 3 hours. Acetic acid was then distilled off fromthe reaction mixture and 30 ml of ice water were added to the paleyellow residue. The insoluble matter was collected by filtration andthen dried in air. The title compound was obtained as a pale yellowsolid. Yield: 421 mg (86%). Its physicochemical properties are shown inTable 5.

The other compounds shown in Table 2 were also synthesized in accordancewith the above reaction formula. Either the following reactionconditions (a) or (b) were employed.

(a) After reaction for 3-5 hours at 80°-90° C. in acetic acid in aflask, acetic acid was distilled off, and the reaction product wasscraped out from the flask. As an alternative, the reaction product waswashed out with a poor solvent from the flask, collected by filtrationand then dried in air.

(b) After reaction for 5-7 hours at room temperature in 6 N sulfuricacid, the insoluble matter was collected by filtration, washed withwater and then dried in air [see Chem. Ber., 115, 3706-18 (1982].

The following yields were achieved under the respective reactionconditions:

    ______________________________________                                        Compound No.                                                                              Reaction conditions                                                                            Yield (%)                                        ______________________________________                                        II-1        (a) (scraped out)                                                                              98                                               II-2        (b)              93                                               II-3        (b)              76                                               II-4        (b)              96                                               II-5        (b)              40                                               II-6        (b)              85                                               II-7        (a) water        86                                               II-8        (a) H.sub.2 O/methanol (1/1)                                                                   46                                               II-9        (a) H.sub.2 O/ethanol (1/1)                                                                    58                                                II-10      (a) H.sub.2 O/acetonitrile (1/1)                                                               27                                                II-11      (b)              75                                                II-12      (a) H.sub.2 O, CH.sub.2 Cl.sub.2                                                               32                                               ______________________________________                                    

The physiocochemical properties of these compounds are shown in Table 5.

In addition, the physiocochemical properties of the other compoundsshown as preparation intermediates in Table 3 are given in Table 6.

                                      TABLE 5                                     __________________________________________________________________________              Melting                                                             Com-      Point or De-                                                        pound     composition                                                         No. MS (m/e)                                                                            Point (°C.)                                                                   IR (KBr, cm.sup.-1)                                                                             NMR (δ)                              __________________________________________________________________________    II-1                                                                              267   150-155                                                                              3410, 3270, 1590, 1490, 1420, 1340,                              (M.sup.+)    1300, 1280, 1240, 1170, 1120, 1100,                                           900, 870, 780, 730, 680, 600, 590                            II-2                                                                              199   188-190                                                                              3300, 3200, 3250-2700, 1690, 1600,                               (M.sup.+  -44)                                                                      Decomposed                                                                           1560, 1470, 1370, 1320, 1260, 1210,                                           1160, 980, 890, 800, 740, 680, 590, 520                      II-3                                                                              301   164-167                                                                              3410, 3280, 1600, 1470, 1400, 1340,                              (M.sup.+)    1300, 1290, 1270, 1250, 1170, 1140,                                           1110, 880, 830, 600                                          II-4                                                                              233   195-197                                                                              3340, 3260, 3160, 3080, 3300-2700,                               (M.sup.+  -44)                                                                      Decomposed                                                                           1690, 1600, 1560, 1460, 1380, 1370,                                           1340, 1310, 1260, 1230, 1160,                                                 830, 770, 590                                                II-5                                                                              281   168-169                                                                              3310, 3230, 1625, 1610, 1520, 1490,                                                             d.sub.6 -DMSO: 2.500(3H, s) 7.109(1H,                                         dd, 8.5Hz, 1.8Hz)                              (M.sup.+ )                                                                          Decomposed                                                                           1410, 1350, 1290, 1250, 1160, 1140,                                                             7.270(1H, d, 8.5Hz) 7.341(1H, q,                                              4.88Hz) 7.377(2H, s)                                        1120, 1070, 900, 830, 780, 700, 610, 510                                                        7.614(1H, d, 1.8Hz) 11.263(1H, s)          II-6      172-173                                                                              3370, 3250, 3100-2300, 1670, 1550,                                                              d.sub.6 -DMSO: 2.507(3H, s) 7.138(1H,                                         s) 7.183(1H, dd, 8.54Hz,                             Decomposed                                                                           1490, 1440, 1320, 1290, 1240, 1180,                                                             2.44Hz) 7.272(1H, d, 8.54Hz) 7.367(2H,                                        s) 7.657(1H, d,                                             1150, 1140, 870, 600                                                                            2.44Hz) 11.324(1H, s) H of COOH was                                           not observed.                              II-7                                                                              325   227-230                                                                              3350, 3280, 3250, 2950, 1700, 1690,                              (M.sup.+)                                                                           Decomposed                                                                           1600, 1540, 1440, 1330, 1300, 1280,                                           1260, 1170, 1150, 1110, 870, 780,                                             760, 590                                                     II-8                                                                              257   197-200                                                                              3300-2800br, 3250, 3150, 3080, 1710,                                                            d.sub.6 -DMSO: 3.823(3H, s) 7.216(2H,                                         s) 7.238(1H, s)                                (M.sup.+  -44)                                                                      Decomposed                                                                           1690, 1600, 1560, 1320, 1300, 1270,                                                             7.299(1H, dd, 7.93Hz, 1.83Hz)                                                 7.737(1H, d, 7.93Hz)                                        1240, 1160, 1120, 850, 830, 780, 590                                                            7.743(1H, d, 1.83Hz) 11.666(1H,                                               s)12.645br(1H, s)                          II-9                                                                              339   238-241                                                                              3350, 3280, 3250, 1680, 1600, 1330,                              (M.sup.+)                                                                           Decomposed                                                                           1300, 1280, 1240, 1170, 1150, 1110,                                           880, 780, 700, 600                                            II-10                                                                            271   138-140                                                                              3300-2700, 3250, 1701, 1690, 1600,                               (M.sup.+  -44)                                                                      Decomposed                                                                           1560, 1320, 1270, 1240, 1160, 1120,                                           820, 780                                                      II-11                                                                            353   224-226                                                                              3400, 3280, 3200-2700, 1670, 1610,                                                              d.sub.6 -DMSO: 7.216(1H, dd, 8.55Hz,                                          2.44Hz) 7.497(1H, d,                           (M.sup.+  -18)                                                                      Decomposed                                                                           1510, 1460, 1340, 1270, 1170, 1020,                                                             8.55Hz) 7.575(2H, s) 7.731(1H, d,                                             2.44Hz) 8.764(1H, s)                                                          11.612(1H, s) H of COOH was not                                               observed.                                   II-12                                                                            377   239-241                                                                              3380, 3260, 3200-2700, 1710, 1685,                                                              d.sub.6 -DMSO: 3.823(3H, s)                                                   7.223-7.760(5H, m) 8.822(1H, s)                (M.sup.+  -18)                                                                      Decomposed                                                                           1610, 1550, 1530, 1520, 1330, 1290,                                                             11.832(1H, s) H of COOH was not                                               observed.                                                   1270, 1250, 1170, 1160, 1120, 1020,                                           745, 700                                                     __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________                Melting                                                                       Point or                                                          Compound    Decomposition                                                     No.   MS (m/e)                                                                            Point (°C.)                                                                    IR (KBr, cm.sup.-1)                                                                          NMR (δ)                              __________________________________________________________________________    V-1   187   113-116 3360, 3350, 3300, 3220, 1500,                                                 1470, 1340, 1330, 1290, 1140,                                                 1090, 780, 680, 580, 510                                  V-2   221   155-158 3370, 3330, 3130, 2970, 1590,                                         Decomposed                                                                            1560, 1460, 1330, 1270,                                                       1160, 970, 830, 740, 690, 590,                                                550, 510                                                  V-3   201   161-164 3300, 3250, 3010, 1610, 1490,                                                                d.sub.6 -DMSO: 2.409(3H, s)                                    1300, 1160, 1140, 920, 820,                                                                  4.025br(2H, s) 6.840                                           690, 600, 520  (1H, dd, 8.5Hz, 1.8Hz)                                                        6.901(1H, s) 7.048(1H,                                                        d, 8.5Hz) 7.148(2H, s)                                                        7.349(1H, d, 1.8Hz)                        V-4   245   168-170 3350, 3310, 3250, 1680, 1630,                                                 1590, 1440, 1350, 1330, 1300,                                                 1270, 1170, 1160, 780, 700, 600                           V-5   259   122-124 3320, 3270, 2980, 1700, 1590,                                         Decomposed                                                                            1370, 1320, 1300, 1270, 1250,                                                 1150, 1120, 770, 740, 700                                 __________________________________________________________________________

Compounds available in a similar manner to Synthesis Example 2 aresummarized in Table 7.

                  TABLE 7                                                         ______________________________________                                         ##STR14##                                                                    Compound                                                                      No.     R.sup.1      R.sup.2   X.sup.1                                                                             X.sup.2                                                                             Z                                  ______________________________________                                        I-21    CF.sub.3     H         CH.sub.3                                                                            OCH.sub.3                                                                           N                                  I-22    CF.sub.3     H         OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  I-23    CF.sub.3     Cl        CH.sub.3                                                                            OCH.sub.3                                                                           N                                  I-24    CF.sub.3     Cl        OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  I-25    CF.sub.3     CH.sub.3  CH.sub.3                                                                            OCH.sub.3                                                                           N                                  I-26    CF.sub.3     CH.sub.3  OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  I-27    CF.sub.3     COOC.sub.2 H.sub.5                                                                      CH.sub.3                                                                            OCH.sub.3                                                                           N                                  I-28    CF.sub.3     COOC.sub.2 H.sub.5                                                                      OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  I-29    COOH         H         OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  I-30    COOH         Cl        OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  I-31    COOH         CH.sub.3  CH.sub.3                                                                            OCH.sub.3                                                                           N                                  I-32    COOH         COOCH.sub.3                                                                             OCH.sub. 3                                                                          OCH.sub.3                                                                           N                                  I-33    COOH         COOC.sub.2 H.sub.5                                                                      CH.sub.3                                                                            OCH.sub.3                                                                           N                                  I-34    COOH         COOC.sub.2 H.sub.5                                                                      OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  I-35    CClCClCOOH   H         OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  I-36    CClCClCOOH   Cl        CH.sub.3                                                                            OCH.sub.3                                                                           N                                  I-37    CClCClCOOH   CH.sub.3  OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  I-38    CClCClCOOH   COOCH.sub.3                                                                             CH.sub.3                                                                            OCH.sub.3                                                                           N                                  I-39    CClCClCOOH   COOCH.sub.3                                                                             OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  I-40    CClCClCOOH   COOC.sub.2 H.sub.5                                                                      OCH.sub.3                                                                           OCH.sub.3                                                                           N                                  ______________________________________                                    

Formulation examples and tests will hereinafter be described. It shouldbe borne in mind that the vehicles (diluents) and aids, their mixingratios and effective components can vary in wide ranges, respectively.

FORMULATION EXAMPLE 1 Wettable Powder

    ______________________________________                                        Compound (Compound No. I-7)                                                                            50 parts                                             A salt of ligninsulfonic acid                                                                          5 parts                                              A salt of alkylsulfonic acid                                                                           3 parts                                              Diatomaceous earth       42 parts                                             ______________________________________                                    

The above ingredients are mixed and ground into a wettable powder. Forapplication, it is diluted with water.

FORMULATION EXAMPLE 2 Emulsion

    ______________________________________                                        Compound (Compound No. I-11)                                                                           25 parts                                             Xylene                   65 parts                                             Polyoxyethylene alkylaryl ether                                                                        10 parts                                             ______________________________________                                    

The above ingredients are mixed intimately into an emulsion. Forapplication, it is diluted with water.

FORMULATION EXAMPLE 3 Granule

    ______________________________________                                        Compound (Compound No. I-17)                                                                           8 parts                                              Bentonite                40 parts                                             Clay                     45 parts                                             A salt of ligninsulfonic acid                                                                          7 parts                                              ______________________________________                                    

The above ingredients are mixed intimately and after the addition ofwater, were kneaded and then formed into granules by an extrudinggranulator. They were then dried to provide a granular formulation,namely, a granule.

TEST 1 Test on Herbicidal Activity by Foliar Application

Herbicidal solutions of each test compound, which had been prepared bydissolving at predetermined concentrations such a wettable powder of thetest compound as that described in the above formulation example, andsprayed at dosages of 10 g/ha and 100 g/ha over foliar parts ofAmaranthus retroflexus (Redroot pigweed), Bidens pilosa (Commonblackjack), Sinapis aryensis (Wild mustard), Stellaria media (Commonchickweed), Cassia obtusifolia (Sicklepod), Solanum nigrum (Blacknightshade, Abutilon theophrasti (Velvetleaf), Convolvulus arvensis(Field bindweed), Matricaria chamomilla (Wild chamomile), Setrariaviridis (Green foxtail), Echinochloa frumenraceum (Barnyard grass),Avena fatua(Wild oat), and Digitaria adscendens (Henry crabgrass) whichhad been allowed to grow individually to 2-4 leaf stage in pots.Fourteen days later after spraying of the test compound, its herbicidalactivity was evaluated in accordance with the below-described system.The results are summarized in Table 8.

RANKING SYSTEM Herbicidal activity

0: No effects

1: less than 31% of total kill

2: 31-50% of total kill

3: 51-70% of total kill

4: 71-90% of total kill

5: 91-100% of total kill

                                      TABLE 8                                     __________________________________________________________________________    Compound                                                                            application                                                             No.   dosage (g/ha)                                                                        A.r.                                                                             B.p.                                                                             S.a.                                                                             S.m.                                                                             C.o.                                                                             S.n.                                                                             A.t                                                                              C.a.                                                                             M.c.                                                                             S.v.                                                                             E.f.                                                                             A.f.                                                                             D.a.                         __________________________________________________________________________    I-1    10    5  4  5  5  1  0  3  0  2  0  0  0  0                                  100    5  5  5  5  5  1  5  1  5  1  2  5  1                            I-2    10    5  4  5  5  2  0  5  1  5  2  0  0  0                                  100    5  5  5  5  5  4  5  5  5  4  4  0  0                            I-3    10    5  5  5  5  5  3  5  4  5  0  4  0  3                                  100    5  5  5  5  5  4  5  5  5  4  5  3  3                            I-4    10    5  5  5  5  5  1  5  1  5  0  0  2  0                                  100    5  5  5  5  5  5  5  5  5  5  5  5  3                            I-5    10    5  5  5  5  5  4  5  0  5  0  2  0  0                                  100    5  5  5  5  5  5  5  3  5  2  5  0  2                            I-6    10    5  5  5  5  5  5  5  5  5  5  3  2  2                                  100    5  5  5  5  5  5  5  5  5  5  4  3  3                            I-7    10    5  5  5  5  5  5  5  4  5  5  5  3  0                                  100    5  5  5  5  5  5  5  5  5  5  5  5  5                            I-8    10    5  5  5  5  5  5  5  5  5  5  5  5  0                                  100    5  5  5  5  5  5  5  5  5  5  5  5  5                            I-9    10    5  5  5  5  5  5  5  5  5  2  2  4  0                                  100    5  5  5  5  5  5  5  5  5  5  5  5  4                            I-10   10    5  5  5  5  5  5  5  5  5  3  4  4  0                                  100    5  5  5  5  5  5  5  5  5  5  5  5  3                            I-11   10    5  5  5  5  5  5  5  3  5  4  5  0  0                                  100    5  5  5  5  5  5  5  5  5  5  5  5  2                            I-12   10    5  5  5  5  5  5  5  5  5  5  4  0  0                                  100    5  5  5  5  5  5  5  5  5  5  5  5  3                            I-13   10    5  5  5  5  5  5  5  5  5  5  5  5  0                                  100    5  5  5  5  5  5  5  5  5  5  5  5  5                            I-14   10    5  5  5  5  5  5  5  5  5  5  5  5  5                                  100    5  5  5  5  5  5  5  5  5  5  5  5  5                            I-15   10    5  5  5  5  5  5  5  5  5  5  4  5  1                                  100    5  5  5  5  5  5  5  5  5  5  5  5  5                            I-16   10    5  5  5  5  5  5  5  5  5  4  2  2  0                                  100    5  5  5  5  5  5  5  5  5  5  5  5  3                            I-17   10    5  5  5  5  5  5  5  5  5  5  1  2  0                                  100    5  5  5  5  5  5  5  5  5  5  5  5  5                            I-18   10    5  5  5  5  3  3  5  5  5  2  0  0  0                                  100    5  5  5  5  5  5  5  5  5  4  4  4  0                            I-19   10    5  5  5  5  4  4  5  5  5  3  1  1  0                                  100    5  5  5  5  5  5  5  5  5  4  4  4  1                            I-20   10    5  5  5  5  5  5  5  5  5  4  2  2  0                                  100    5  5  5  5  5  5  5  5  5  5  5  5  4                            __________________________________________________________________________     Note)                                                                         A.r.: Amaranthus retroflexus                                                  B.p.: Bidens pilosa                                                           S.a.: Sinapis arvensis                                                        S.m.: Stellaria media                                                         C.o.: Cassia obtusifolia                                                      S.n.: Solanum nigrum                                                          A.t.: Abutilon theophrasti                                                    C.a.: Convolvulus arevensis                                                   M.c.: Matricaria chamomilla                                                   S.v.: Setaria viridis                                                         E.f.: Echinochloa frumentaceum                                                A.f.: Aveno fatua                                                             D.a.: Digitaria adscendens                                               

TEST 2 Germination Test of Seeds

Two sheets of filter paper were placed in a superposed relation in eachof Petri dishes having a diameter of 9 cm. Water suspensions of eachtest compound (concentrations of the active ingredient 1 ppm and 50 ppm)were separately poured in an amount of 5 ml per dish into the Petridishes. Seeds of Amaranthus retroflexus (Redroot pigweed), Bidens pilosa(Common blackjack), Matricaria chamomilla (Wild chamomile), Solanumnigrum (Black nightshade), Echinochloa oxyzicola (Barnyard grass),Cyperus iria (Rice flatsedge) and Setaria viridis (Green foxtail) wereplaced at a rate of 10 seeds per dish in the Petri dishes. They werethereafter allowed to germinate in a constant-temperature chamber at 28°C. Fourteen days later after placement in the Petri dishes, the degreesof germination and growth inhibition were observed visually. Theobservation results were ranked in accordance with the below-described6-stage system. The results are summarized in Table 9.

GROWTH INHIBITION RATE

0: No inhibition

1: less than 31%

2: 31-50%

3: 51-70%

25 4: 71-90%

5: 91-100%

                  TABLE 9                                                         ______________________________________                                        Com-  Concen-                                                                 pound tration                                                                 No.   (ppm)    A.r.   B.p. M.c. S.n. E.o. C.i. S.v.                           ______________________________________                                        I-1    1       3      3    4    1    4    3    2                                    50       5      4    4    5    4    4    4                              I-2    1       3      0    3    3    0    3    1                                    50       4      4    4    4    3    4    5                              I-3    1       3      3    4    2    4    3    4                                    50       4      3    4    5    5    4    5                              I-4    1       4      3    4    3    4    3    3                                    50       4      4    4    5    5    4    5                              I-5    1       2      0    2    2    2    3    2                                    50       3      3    3    3    5    4    5                              I-6    1       3      2    3    2    3    2    3                                    50       5      4    3    4    4    3    4                              I-7    1       3      3    4    3    4    5    5                                    50       3      4    4    5    5    5    5                              I-8    1       4      3    5    3    5    5    5                                    50       4      4    5    3    5    5    5                              I-9    1       4      4    5    4    4    4    3                                    50       5      4    5    4    5    5    5                              I-10   1       3      3    5    4    1    4    4                                    50       4      4    5    4    4    4    5                              I-11   1       2      1    1    5    1    2    1                                    50       4      4    3    5    3    4    4                              I-12   1       2      0    4    1    1    3    1                                    50       3      2    4    5    2    4    3                              I-13  1        3      2    4    1    2    2    2                                    50       4      4    4    5    4    4    4                              I-14   1       2      1    1    1    1    1    1                                    50       3      3    4    4    3    4    4                              I-15   1       3      2    3    2    1    4    3                                    50       4      4    5    3    4    4    4                              I-16   1       1      0    3    2    0    2    1                                    50       3      3    4    4    4    4    5                              I-17   1       1      1    2    2    0    2    0                                    50       2      2    3    4    1    4    3                              I-18   1       3      2    3    3    4    4    4                                    50       4      3    5    3    5    4    5                              I-19   1       3      2    4    2    3    3    4                                    50       4      3    4    4    5    4    4                              I-20   1       1      1    3    2    0    2    1                                    50       3      3    4    4    3    4    4                              ______________________________________                                         Note)                                                                         A.r.: Amaranthus retroflexus                                                  B.p.: Bidens pilosa                                                           M.c.: Matricaria chamomilla                                                   S.n.: Solanum nigrum                                                          E.o.: Echinochloa oryzicola                                                   C.i.: Cyperus iria                                                            S.v.: Setaria viridis                                                    

I claim:
 1. An N-substituted-3-(substitutedhydrazino)-benzenesulfonamide derivative of the formula (I): ##STR15##wherein R¹ is CF₃, COOH or CC1═CC1COOH, R² is H, Cl, C₁ -C₃ alkyl or C₁-C₄ alkoxycarbonyl; Z is CH; X¹ is C₁ -C₃ alkyl, C₁ -C₃ akoxyl or Cl;and X² is C₁ -C₃ alkyl or C₁ -C₃ alkoxyl.
 2. A derivative of claim 1,wherein R¹ is CF₃, COOH or CCl═CC1COOH, R² is H, Cl, CH₃, COOCH₃ orCOOC₂ H₅, Z is CH, X¹ is OCH₃, and X² is OCH₃.
 3. A derivative of claim1, wherein R¹ is CF₃ or COOH, R² is COOCH₃, Z is CH, X¹ is Cl, and X² isOCH₃.
 4. A derivative of claim 1, wherein R¹ is CF₃ or COOH, R² isCOOCH₃, Z is CH, X¹ is CH₃ or OCH₃, and X² is CH₃.
 5. A derivative ofclaim 1, wherein R₂ is Cl or COCH₃, Z is CH, X¹ is CH₃ or OCH₃ and X² isOCH₃.
 6. A herbicidal composition comprising a herbicidally effectiveamount of an N-substituted-3-(substituted hydrazino)benzenesulfonamidederivative of claim 1 and an agronomically-acceptable vehicle ordiluent.
 7. A method for the control of monocotyledonous ordicotyledonous weeds on an agricultural or non-agricultural land, whichcomprises applying to the agricultural or non-agricultural land onN-substituted-3-(substituted hydrazino)benzenesulfonamide derivative ofclaim 1 or a herbicidal composition comprising said derivative.